EP0623638B1 - Oxidized poly(arylene sulfide) - Google Patents
Oxidized poly(arylene sulfide) Download PDFInfo
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- EP0623638B1 EP0623638B1 EP94106565A EP94106565A EP0623638B1 EP 0623638 B1 EP0623638 B1 EP 0623638B1 EP 94106565 A EP94106565 A EP 94106565A EP 94106565 A EP94106565 A EP 94106565A EP 0623638 B1 EP0623638 B1 EP 0623638B1
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- ozone
- reaction
- oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0286—Chemical after-treatment
- C08G75/0295—Modification with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/18—Polysulfoxides
Definitions
- the invention relates to polyarylene sulfide / sulfoxides and polyarylene sulfoxides have a defined sulfur / oxygen ratio.
- Polyarylene sulfides have been known for some time. Because of their high These are heat resistance and good chemical resistance Polymers used for highly stressed components. With some However, applications are subject to higher material requirements. Is special an increase in the glass transition temperature of the polymers is often desirable. This should be achieved by a polymer-analogous oxidation of Polyphenylene sulfide to polyphenylene sulfoxide in acetic acid with concentrated Nitric acid for 24 hours at 0 to +5 ° C (US 3,303,007). The However, the property values given for the polymer formed indicate this indicates that no polymer with a sulfur / oxygen ratio of 1 to 1 was obtained because the heat resistance values were not increased were. Under "polymer analog" is the conversion of a polymer into a to understand other.
- the object of the invention is a process for the production of oxidation products to develop polyarylene sulfides, the products being a defined Should have sulfur / oxygen ratio and from the prior art known side reactions should be avoided.
- the invention relates to a process for the production of oxidation products of polyarylene sulfides with repeating units of the formula in which a connection with recurring units of the formula is obtained in which the sulfur / oxygen ratio is 1: 0.1 to 1: 1, the sum of a and b always being 1, with the proviso that a is zero when b is 1.
- Useful polymers of formula (I) are generally 1,4-linked Polyarylene sulfides that have a 1,2- and / or 1,3-linkage up to a proportion of 30 mol% may have on the aromatic nucleus.
- PPS polyphenylene sulfide
- polymers are suitable for the invention which have a medium Molecular weight from 4,000 to 200,000, preferably from 10,000 to 150,000, in particular 25,000 to 100,000, determined by GPC.
- the particle size of the polymers used is generally in the range from 5 ⁇ 10 -6 to 500 ⁇ 10 -6 m, preferably 10 ⁇ 10 -6 to 300 ⁇ 10 -6 m and in particular 10 ⁇ 10 -6 to 200 ⁇ 10 -6 m.
- the reaction temperatures are in the range from -10 to +80 ° C, preferably 0 to 50 ° C.
- the response time required depends on the ozone supply and the chosen reactor type and is generally 1 minute to 2 Hours, preferably 5 to 90 minutes and in particular 5 to 60 minutes. However, it is also possible to optimize the reaction conditions to come at times under a minute.
- the oxidation according to the invention is carried out in an ozone-containing gas stream carried out in which the ozone generally in a concentration of 0.1 to 9 vol .-%, preferably 2 to 6 vol .-% is included.
- a carrier gas for the Ozone is made up of oxygen or inert gases such as nitrogen or mixtures this suitable. Dried air can also produce ozone be used.
- the ozone is generally used in engineering known methods, e.g. generated by silent electrical discharge.
- the reaction is carried out in a temperature-controlled, suitable for fumigation reactions Reaction vessel carried out.
- liquid compounds e.g. Water, lower aliphatic Alcohols and carboxylic acids each with 1-6, preferably 1-3 carbon atoms in the Alkyl group, the esters from the two classes of compounds mentioned above, Hydrocarbons with 1-12 C atoms halogenated with chlorine or fluorine can be and mixtures of the compounds mentioned.
- Mineral acids are suitable, e.g. concentrated sulfuric acid.
- Solvent mixtures can be added with a mineral acid, e.g. Sulfuric acid, be beneficial.
- the suspension medium generally dissolves no or only very little Amounts of the polymer, however, it acts as a heat and ozone transmitter and has a controlling influence on selectivity.
- the reaction can also not in liquid phase must be carried out, however, then for a lively Mixing of the polymer powder can be ensured, otherwise at the location of the Local overheating (hot spot) can occur, which can has a negative effect on the oxidation selectivity.
- the compounds obtained according to the invention can either be process thermoplastic or can for example by common Sintering processes are processed, but this depends on their Melting points.
- the first group can be the usual for thermoplastics Processing methods, e.g. B. injection molding or extrusion, in mold and Functional parts are transferred.
- the molding compositions can also be known powdery fillers, such as chalk, talc, clay, mica, and / or fibrous Reinforcing agents such as glass and carbon fibers, whiskers, and others usual additives and processing aids, e.g. Lubricants, release agents, Antioxidants, UV stabilizers.
- Such parts are used as highly stressable functional components, for example in aircraft and Automotive and chemical apparatus engineering.
- the second group i.e. the polymers that can be processed by sintering processes, is used for functional parts with a high temperature and Chemical exposure.
- Tg means the glass transition temperature
- Tm is the Melting point
- the sulfur / oxygen ratio of the polymer obtained was 1: 1.
- the suspension was gassed through a glass frit with an ozone-containing gas stream (flow rate 180-200 l / h) with a concentration of 50 to 100 grams of ozone per cubic meter of gas.
- the reaction was stopped after 48 g of ozone had been taken up, because at this point there was a clear drop in the reaction rate.
- the polymer powder was then filtered off, washed several times with small amounts of water and then dried at 30 mbar and 50-100 ° C. Only sulfoxide groups can be seen in the IR spectrum. The sulfur / oxygen ratio in the polymer obtained was 1: 0.51.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
Die Erfindung betrifft Polyarylensulfid/sulfoxide und Polyarylensulfoxide, die ein definiertes Schwefel/Sauerstoffverhältnis aufweisen.The invention relates to polyarylene sulfide / sulfoxides and polyarylene sulfoxides have a defined sulfur / oxygen ratio.
Polyarylensulfide sind seit geraumer Zeit bekannt. Aufgrund ihrer hohen Wärmeformbeständigkeit und guten Chemikalienresistenz werden diese Polymere für hochbeanspruchte Bauteile herangezogen. Bei einigen Anwendungen werden jedoch höhere Materialanforderungen gestellt. Speziell ist häufig eine Anhebung der Glastemperatur der Polymeren wünschenswert. Dies soll erreicht werden durch eine polymeranaloge Oxidation von Polyphenylensulfid zu Polyphenylensulfoxid in Essigsäure mit konzentrierter Salpetersäure während 24 Stunden bei 0 bis +5 °C (US 3,303,007). Die angeführten Eigenschaftswerte für das gebildete Polymer deuten jedoch darauf hin, daß kein Polymeres mit einem Schwefel/Sauerstoff-Verhältnis von 1 zu 1 erhalten wurde, da die Werte für die Wärmeformbeständigkeit nicht erhöht waren. Unter "polymeranalog" ist die Umwandlung eines Polymeren in ein anderes zu verstehen. Polyarylene sulfides have been known for some time. Because of their high These are heat resistance and good chemical resistance Polymers used for highly stressed components. With some However, applications are subject to higher material requirements. Is special an increase in the glass transition temperature of the polymers is often desirable. This should be achieved by a polymer-analogous oxidation of Polyphenylene sulfide to polyphenylene sulfoxide in acetic acid with concentrated Nitric acid for 24 hours at 0 to +5 ° C (US 3,303,007). The However, the property values given for the polymer formed indicate this indicates that no polymer with a sulfur / oxygen ratio of 1 to 1 was obtained because the heat resistance values were not increased were. Under "polymer analog" is the conversion of a polymer into a to understand other.
Die Umsetzung von Polyphenylensulfid suspendiert in Essigsäureanhydrid unter Verwendung von 70%iger Salpetersäure ist ebenfalls bekannt (US 3,303,087 und US 3,326,865). Allerdings bestehen bei diesen Verfahren die Möglichkeiten einer elektrophilen Addition und des aciden Angriffs der starken mineralischen Säure an der Thioetherbindung bei langen Reaktionszeiten. Der acide Angriff führt zu einem Kettenabbau. Weiter hat auch die lange Reaktionszeit einen negativen Einfluß auf das Molekulargewicht.The reaction of polyphenylene sulfide suspended in acetic anhydride The use of 70% nitric acid is also known (US 3,303,087 and US 3,326,865). However, there is a possibility with these methods electrophilic addition and acidic attack of the strong mineral acid the thioether bond with long reaction times. The acid attack leads to one Chain degradation. The long reaction time also has a negative impact the molecular weight.
Aufgabe der Erfindung ist es, ein Verfahren zur Herstellung von Oxidationsprodukten von Polyarylensulfiden zu entwickeln, wobei die Produkte ein definiertes Schwefel/Sauerstoffverhältnis aufweisen sollen und die aus dem Stand der Technik bekannten Nebenreaktionen vermieden werden sollen.The object of the invention is a process for the production of oxidation products to develop polyarylene sulfides, the products being a defined Should have sulfur / oxygen ratio and from the prior art known side reactions should be avoided.
Die Erfindung betrifft ein Verfahren zur Herstellung von Oxidationsprodukten von
Polyarylensulfiden mit wiederkehrenden Einheiten der Formel
Die Oxidation von polymeren Arylensulfiden mit Ozon führt bei hoher Selektivität zur Bildung von Polyarylensulfoxiden. Dies ist um so mehr überraschend, als Ozon ein extrem starkes Oxidationsmittel ist. Durch entsprechenden Einsatz der Menge an Ozon ist es möglich, entweder die Schwefelbindung vollständig in die Sulfoxidbindung zu überführen oder jedes beliebige S/O-Verhältnis in der Polymerkette zu erzielen. Dabei hat die Wahl des eingesetzten Suspensionsmittels entscheidenden Einfluß.The oxidation of polymeric arylene sulfides with ozone leads to high Selectivity to form polyarylene sulfoxides. This is all the more so surprising when ozone is an extremely powerful oxidizing agent. By appropriate use of the amount of ozone it is possible to either the To completely convert the sulfur bond into the sulfoxide bond or each to achieve any S / O ratio in the polymer chain. The choice of used suspension medium decisive influence.
Verwendbare Polymere der Formel (I) sind im allgemeinen 1,4-verknüpfte Polyarylensulfide, die bis zu einem Anteil von 30 Mol-% eine 1,2- und/oder 1,3-Verknüpfung am aromatischen Kern aufweisen können.Useful polymers of formula (I) are generally 1,4-linked Polyarylene sulfides that have a 1,2- and / or 1,3-linkage up to a proportion of 30 mol% may have on the aromatic nucleus.
Bevorzugt ist Polyphenylensulfid (PPS), dessen Herstellungsprozess z. B. in den US-Patenten 3,354,129, 3,919,177, 4,038,262 und 4,282,347 beschrieben ist.Preferred is polyphenylene sulfide (PPS), the manufacturing process z. Tie U.S. Patents 3,354,129, 3,919,177, 4,038,262 and 4,282,347 is.
Für die Erfindung sind im allgemeinen Polymere geeignet, die ein mittleres Molekulargewicht von 4 000 bis 200 000, vorzugsweise von 10 000 bis 150 000, insbesondere 25 000 bis 100 000, bestimmt durch GPC, aufweisen. In general, polymers are suitable for the invention which have a medium Molecular weight from 4,000 to 200,000, preferably from 10,000 to 150,000, in particular 25,000 to 100,000, determined by GPC.
Die Teilchengröße der eingesetzten Polymere liegt im allgemeinen im Bereich von 5×10-6 bis 500×10-6 m, vorzugsweise 10×10-6 bis 300×10-6 m und insbesondere 10×10-6 bis 200×10-6 m.The particle size of the polymers used is generally in the range from 5 × 10 -6 to 500 × 10 -6 m, preferably 10 × 10 -6 to 300 × 10 -6 m and in particular 10 × 10 -6 to 200 × 10 -6 m.
Die Reaktionstemperaturen liegen im Bereich von -10 bis +80 °C, vorzugsweise 0 bis 50 °C. Die erforderliche Reaktionszeit hängt von dem Angebot an Ozon und dem gewählten Reaktortyp ab und beträgt im allgemeinen 1 Minute bis 2 Stunden, vorzugsweise 5 bis 90 Minuten und insbesondere 5 bis 60 Minuten. Allerdings ist es auch möglich, bei einer Optimierung der Reaktionsbedingungen auf Zeiten unter einer Minute zu kommen.The reaction temperatures are in the range from -10 to +80 ° C, preferably 0 to 50 ° C. The response time required depends on the ozone supply and the chosen reactor type and is generally 1 minute to 2 Hours, preferably 5 to 90 minutes and in particular 5 to 60 minutes. However, it is also possible to optimize the reaction conditions to come at times under a minute.
Die Oxidation gemäß der Erfindung wird in einem ozonhaltigen Gasstrom durchgeführt, in dem das Ozon im allgemeinen in einer Konzentration von 0,1 bis 9 Vol.-%, vorzugsweise 2 bis 6 Vol.-% enthalten ist. Als Trägergas für das Ozon sind Sauerstoff oder Inertgase, wie Stickstoff oder auch Gemische aus diesen geeignet. Ebenfalls kann getrocknete Luft bei der Erzeugung des Ozons eingesetzt werden. Das Ozon wird im allgemeinen durch in der Technik bekannte Methoden, z.B. durch stille elektrische Entladung, erzeugt.The oxidation according to the invention is carried out in an ozone-containing gas stream carried out in which the ozone generally in a concentration of 0.1 to 9 vol .-%, preferably 2 to 6 vol .-% is included. As a carrier gas for the Ozone is made up of oxygen or inert gases such as nitrogen or mixtures this suitable. Dried air can also produce ozone be used. The ozone is generally used in engineering known methods, e.g. generated by silent electrical discharge.
Die Reaktion wird in einem temperierbaren, für Begasungsreaktionen geeigneten Reaktionsgefäß durchgeführt. Dies kann beispielsweise ein begaster Rührkessel oder eine Blasensäule sein.The reaction is carried out in a temperature-controlled, suitable for fumigation reactions Reaction vessel carried out. For example, a fumigated stirred tank or be a bladder column.
Als Suspensionsmedien sind alle unter den Reaktionsbedingungen als inert geltende flüssige Verbindungen geeignet, z.B. Wasser, niedere aliphatische Alkohole und Carbonsäuren mit jeweils 1-6, vorzugsweise 1-3 C-Atomen in der Alkylgruppe, die Ester aus den beiden vorgenannten Verbindungsklassen, Kohlenwasserstoffe mit 1-12 C-Atomen, die mit Chlor oder Fluor halogeniert sein können und Gemische aus den genannten Verbindungen. Auch Mineralsäuren sind geeignet, z.B. konzentrierte Schwefelsäure. In protischen Lösungsmitteln oder protische Lösungsmittel enthaltenden Lösungsmittelgemischen kann der Zusatz einer Mineralsäure, z.B. Schwefelsäure, von Vorteil sein.As suspension media, all are inert under the reaction conditions applicable liquid compounds, e.g. Water, lower aliphatic Alcohols and carboxylic acids each with 1-6, preferably 1-3 carbon atoms in the Alkyl group, the esters from the two classes of compounds mentioned above, Hydrocarbons with 1-12 C atoms halogenated with chlorine or fluorine can be and mixtures of the compounds mentioned. Also Mineral acids are suitable, e.g. concentrated sulfuric acid. In protic Solvents or protic solvents Solvent mixtures can be added with a mineral acid, e.g. Sulfuric acid, be beneficial.
Beispielsweise wird in Methylenchlorid in kurzer Zeit eine vollständige Oxidation zum Sulfoxid erreicht. Dagegen wird bei Einsatz von niederen aliphatischen Carbonsäuren mit einem Zusatz einer Mineralsäure nur eine teilweise Oxidation erzielt, da die Aufnahmegeschwindigkeit des Ozons bei Erreichen eines Schwefel/Sauerstoffverhältnisses von 1:0,5 deutlich absinkt. Es ist zwar möglich, auch hier eine vollständige Oxidation zu erreichen, jedoch sind dafür unwirtschaftlich lange Reaktionszeiten nötig.For example, complete oxidation occurs in methylene chloride in a short time reached to sulfoxide. In contrast, when using lower aliphatic Carboxylic acids with the addition of a mineral acid only a partial oxidation achieved because the absorption rate of the ozone when reaching a Sulfur / oxygen ratio drops significantly from 1: 0.5. It is possible to achieve complete oxidation here too, but are in favor uneconomically long reaction times necessary.
Das Suspensionsmedium löst im allgemeinen keine oder nur sehr geringe Mengen des Polymeren, es fungiert jedoch als Wärme- und Ozonüberträger und hat steuernden Einfluß auf die Selektivität. Die Reaktion kann zwar auch in nicht flüssiger Phase durchgeführt werden, jedoch muß dann für eine lebhafte Durchmischung des Polymerpulvers gesorgt werden, da sonst an der Stelle des Ozoneintrags eine lokale Überhitzung (hot-spot) stattfinden kann, welche sich negativ auf die Oxidationsselektivität auswirkt.The suspension medium generally dissolves no or only very little Amounts of the polymer, however, it acts as a heat and ozone transmitter and has a controlling influence on selectivity. The reaction can also not in liquid phase must be carried out, however, then for a lively Mixing of the polymer powder can be ensured, otherwise at the location of the Local overheating (hot spot) can occur, which can has a negative effect on the oxidation selectivity.
Die gemäß der Erfindung erhaltenen Verbindungen lassen sich entweder thermoplastisch verarbeiten oder können beispielsweise durch gängige Sinterverfahren weiterverarbeitet werden, jedoch ist dies abhängig von deren Schmelzpunkten. Die erste Gruppe kann durch die für Thermoplaste gängigen Verarbeitungsmethoden, z. B. Spritzguß oder Extrusion, in Form- und Funktionsteile übergeführt werden. Die Formmassen können auch bekannte pulverförmige Füllstoffe, wie Kreide, Talk, Ton, Glimmer, und/oder faserförmige Verstärkungsmittel, wie Glas- und Kohlenstoffasern, Whiskers, sowie weitere übliche Zusatzstoffe und Verarbeitungshilfsmittel, z.B. Gleitmittel, Trennmittel, Antioxidantien, UV-Stabilisatoren, enthalten. Verwendung finden derartige Teile als hochbeanspruchbare Funktionsbauteile, beispielsweise im Flugzeug- und Automobilbau sowie im chemischen Apparatebau. The compounds obtained according to the invention can either be process thermoplastic or can for example by common Sintering processes are processed, but this depends on their Melting points. The first group can be the usual for thermoplastics Processing methods, e.g. B. injection molding or extrusion, in mold and Functional parts are transferred. The molding compositions can also be known powdery fillers, such as chalk, talc, clay, mica, and / or fibrous Reinforcing agents such as glass and carbon fibers, whiskers, and others usual additives and processing aids, e.g. Lubricants, release agents, Antioxidants, UV stabilizers. Such parts are used as highly stressable functional components, for example in aircraft and Automotive and chemical apparatus engineering.
Die zweite Gruppe, d.h. die durch Sinterverfahren verarbeitbaren Polymere, findet Verwendung bei Funktionsteilen mit einer hohen Temperatur- und Chemikalienbelastung.The second group, i.e. the polymers that can be processed by sintering processes, is used for functional parts with a high temperature and Chemical exposure.
In den Beispielen bedeutet Tg die Glasumwandlungstemperatur, Tm ist der Schmelzpunkt.In the examples, Tg means the glass transition temperature, Tm is the Melting point.
In einem Reaktionsgefäß mit Scheibenrührer wurden 54,1 g eines
Polyphenylensulfid-(PPS)-Pulvers (MW 40 000) mit einem mittleren
Partikeldurchmesser von 20 x 10-6 m, in 400 ml Methylenchlorid suspendiert.
In die Suspension wurde bei Temperaturen von -5 bis -7°C Ozon-haltiges Gas
eingeleitet bis 0,5 Mol Ozon aufgenommen waren (72 Minuten). Die
Ozonkonzentration betrug während der Begasung 51 bis 115 Gramm pro
Kubikmeter Trägergas. Nach der Reaktion wurde das Polymerpulver abgesaugt
und getrocknet. Im Infrarotspektrum konnte nur die ausschließliche Bildung von
Sulfoxid-Gruppen beobachtet werden. Tg: 240°C, Tm: ≥370°C (Zersetzung).
Das Schwefel/Sauerstoff-Verhältnis des erhaltenen Polymers betrug 1:1. The sulfur / oxygen ratio of the polymer obtained was 1: 1.
In einer temperierbaren Blasensäule (5 cm Durchmesser, 120 cm Länge) wurden
216 g eines PPS-Pulvers wie in Beispiel 1 in einer Mischung aus 850 ml Eisessig
und 8,5 ml Schwefelsäure suspendiert. Bei 10 bis 20°C wurde die Suspension
über eine Glasfritte mit einem Ozon-haltigen Gasstrom
(Strömungsgeschwindigkeit 180-200 l/h) mit einer Konzentration von 50 bis
100 Gramm Ozon pro Kubikmeter Gas begast. Nach 80 Minuten wurde die
Reaktion nach Aufnahme von 48 g Ozon abgebrochen, weil sich zu diesem
Zeitpunkt ein deutlicher Abfall der Reaktionsgeschwindigkeit abzeichnete.
Anschließend wurde das Polymerpulver abfiltriert, mehrmals mit kleinen Mengen
Wasser gewaschen und dann bei 30 mbar und 50 - 100°C getrocknet.
Im IR-Spektrum sind nur Sulfoxid-Gruppen zu erkennen.
Das Schwefel/Sauerstoff-Verhältnis bei dem erhaltenen Polymer betrug 1:0,51.216 g of a PPS powder, as in Example 1, were suspended in a mixture of 850 ml of glacial acetic acid and 8.5 ml of sulfuric acid in a bubble column (5 cm in diameter, 120 cm in length) which could be heated. At 10 to 20 ° C, the suspension was gassed through a glass frit with an ozone-containing gas stream (flow rate 180-200 l / h) with a concentration of 50 to 100 grams of ozone per cubic meter of gas. After 80 minutes, the reaction was stopped after 48 g of ozone had been taken up, because at this point there was a clear drop in the reaction rate. The polymer powder was then filtered off, washed several times with small amounts of water and then dried at 30 mbar and 50-100 ° C.
Only sulfoxide groups can be seen in the IR spectrum.
The sulfur / oxygen ratio in the polymer obtained was 1: 0.51.
Claims (5)
- A process for preparing an oxidation product of polyarylene sulfide comprising the recurring unit of the formulain which the sulfur/oxygen ratio is from 1:0.1 to 1:1 and the sum of a and b is always 1, with the proviso that a is zero if b is 1,
by oxidation of polyarylene sulfide having a mean molecular weight of from 4 000 to 200 000 and comprising recurring units of the formulawhich is a 1,4-linked polyarylene sulfide having a proportion of not more than 30% 1,2- and/or 1,3-linkages on the aromatic ring, wherein the oxidation is effected by means of ozone.
- The process as claimed in claim 1, wherein the reaction is carried out at a temperature of from -10°C to +80°C.
- The process as claimed in claim 1 or 2, wherein the reaction is carried out in an ozone-containing gas stream having a concentration of from 0.1% by volume to 9% by volume of ozone.
- The process as claimed in one or more of claims 1 to 3, wherein the reaction is carried out in a suspension.
- The process as claimed in one or more of claims 1 to 4, wherein the reaction time is at least one minute and not more than 2 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4314735 | 1993-05-04 | ||
| DE4314735A DE4314735A1 (en) | 1993-05-04 | 1993-05-04 | Oxidized polyarylene sulfides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0623638A1 EP0623638A1 (en) | 1994-11-09 |
| EP0623638B1 true EP0623638B1 (en) | 2002-06-26 |
Family
ID=6487153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94106565A Expired - Lifetime EP0623638B1 (en) | 1993-05-04 | 1994-04-27 | Oxidized poly(arylene sulfide) |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6020442A (en) |
| EP (1) | EP0623638B1 (en) |
| JP (1) | JPH06329801A (en) |
| DE (2) | DE4314735A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4446495A1 (en) * | 1994-12-23 | 1996-06-27 | Hoechst Ag | Crosslinked molding compositions made from polyarylene sulfides and polyarylene sulfoxides, process for their preparation and their use |
| DE19605359A1 (en) | 1996-02-14 | 1997-08-21 | Hoechst Ag | Plastic foams and processes for their production |
| EP0939142A1 (en) * | 1998-02-27 | 1999-09-01 | Ticona GmbH | Thermal spray powder incorporating an oxidised polyarylene sulfide |
| DE19916495A1 (en) * | 1999-04-12 | 2000-10-19 | Ticona Gmbh | Process for the oxidation of polyarylene sulfide to polyarylene sulfoxide using nitric acid |
| US6949288B2 (en) * | 2003-12-04 | 2005-09-27 | Fiber Innovation Technology, Inc. | Multicomponent fiber with polyarylene sulfide component |
| DE102005010411A1 (en) | 2005-03-07 | 2006-09-14 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Sulfonated poly (arylenes) as hydrolytically and thermo-oxidatively stable polymers |
| WO2020216614A1 (en) | 2019-04-26 | 2020-10-29 | Solvay Specialty Polymers Usa, Llc | Poly(arylene sulfide) and process for its manufacturing |
| CN110564154B (en) * | 2019-10-23 | 2020-07-31 | 四川大学 | Bonded polyarylene sulfide metal composite material with nuclear radiation protection function and preparation method thereof |
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| US3326865A (en) * | 1963-03-27 | 1967-06-20 | Dow Chemical Co | Sulfoxide resins |
| US3303007A (en) * | 1963-09-03 | 1967-02-07 | Union Oil Co | Motor fuel composition |
| US3354129A (en) * | 1963-11-27 | 1967-11-21 | Phillips Petroleum Co | Production of polymers from aromatic compounds |
| CH501028A (en) * | 1968-07-31 | 1970-12-31 | Inventa Ag | Process for the production of linear polysulfones |
| GB1365486A (en) * | 1971-07-05 | 1974-09-04 | Ici Ltd | Aromatic polysulphones |
| US3948865A (en) * | 1974-10-31 | 1976-04-06 | Phillips Petroleum Company | Chemical treatment of arylene sulfide polymers |
| US4383080A (en) * | 1982-04-05 | 1983-05-10 | Phillips Petroleum Company | Process for curing poly(arylene sulfides) |
| WO1991018041A1 (en) * | 1990-05-16 | 1991-11-28 | Solvay & Cie | Functional polymers derived from arylene polysulphides, and production method therefor |
-
1993
- 1993-05-04 DE DE4314735A patent/DE4314735A1/en not_active Withdrawn
-
1994
- 1994-04-27 DE DE59410141T patent/DE59410141D1/en not_active Expired - Fee Related
- 1994-04-27 EP EP94106565A patent/EP0623638B1/en not_active Expired - Lifetime
- 1994-05-02 JP JP6093419A patent/JPH06329801A/en active Pending
-
1996
- 1996-01-11 US US08/585,267 patent/US6020442A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4314735A1 (en) | 1994-11-10 |
| US6020442A (en) | 2000-02-01 |
| JPH06329801A (en) | 1994-11-29 |
| EP0623638A1 (en) | 1994-11-09 |
| DE59410141D1 (en) | 2002-08-01 |
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